CN111909188B - Compound, luminescent material and organic electroluminescent device - Google Patents

Compound, luminescent material and organic electroluminescent device Download PDF

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CN111909188B
CN111909188B CN202010739514.4A CN202010739514A CN111909188B CN 111909188 B CN111909188 B CN 111909188B CN 202010739514 A CN202010739514 A CN 202010739514A CN 111909188 B CN111909188 B CN 111909188B
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reaction
toluene
organic electroluminescent
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CN111909188A (en
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吴建德
丰佩川
胡灵峰
邢其锋
陈义丽
单鸿斌
孙伟
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Yantai Jingshi Materials Genomic Engineering Research Institute
Yantai Xianhua Chem Tech Co ltd
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The embodiment provides a compound of a general formula (I), which can be used for a blue luminescent material. The compound can be used as a blue luminescent material to effectively improve the luminous efficiency of the organic electroluminescent device. The application also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).

Description

Compound, luminescent material and organic electroluminescent device
Technical Field
The present disclosure relates to the field of organic light emitting displays, and in particular, to a compound, a light emitting material, and an organic electroluminescent device including the light emitting material.
Background
Electroluminescent refers to the phenomenon that a luminescent material emits light under the excitation of current (and voltage) under the action of an electric field, and is a luminescent process for directly converting electric energy into light energy. The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advancement of OLED technology in the two fields of illumination and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of the optimized collocation of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
In the most common OLED structures, the following classes of organic materials are typically included: a hole injecting material, a hole transporting material, a light emitting material (containing a host material and a guest material), an electron transporting material, an electron injecting material, and the like. The most important factor determining the luminous efficiency of the OLED is the luminescent material. The luminescent materials are classified into blue, green and red luminescent materials according to the luminescent colors, and it is difficult to develop the blue luminescent materials because the blue luminescent materials require a very wide energy band gap compared to the green and red luminescent materials. OLEDs with blue light emitting materials currently used exhibit lower fluorescence light emission efficiency than phosphorescence.
Disclosure of Invention
In view of the foregoing problems of the prior art, it is an object of the present application to provide a luminescent material to achieve an improvement of the luminescent efficiency of a blue luminescent material in an OLED.
A first aspect of the present application provides a compound of formula (I):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from H,C 6 -C 30 Aryl, C of (2) 3 -C 30 Heteroaryl or NR of (C) 5 R 6 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra, where R 1 、R 2 、R 3 And R is 4 One of which is other than H, or R 1 、R 2 、R 3 And R is 4 Is not H and is the same;
R 5 and R is 6 Each independently selected from C 6 -C 30 Aryl or C of (2) 3 -C 30 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra;
the heteroatoms on the heteroaryl groups are each independently selected from O, S, N;
the Ra's are each independently selected from deuterium, C 1 -C 6 Alkyl, C of (2) 3 -C 6 Cycloalkyl, phenyl, biphenyl, naphthyl or carbazolyl groups.
A second aspect of the present application provides a light-emitting layer host material comprising at least one of the compounds provided herein, wherein R 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 30 Aryl, C of (2) 3 -C 30 Heteroaryl of (a).
A third aspect of the present application provides a light-emitting layer guest material comprising at least one of the compounds provided herein, wherein R 1 、R 2 、R 3 And R is 4 H, NR each independently 5 R 6 。
A fourth aspect of the present application provides an organic electroluminescent device comprising at least one of the light-emitting layer host material and the light-emitting layer guest material provided herein.
A fifth aspect of the present application provides a display device, which includes the organic electroluminescent device provided herein.
The compound provided by the application has good photo-thermal stability and high absorption value. When used as a blue light emitting material, good light emitting efficiency can be achieved in an organic electroluminescent device. The organic electroluminescent device comprises the compound as a blue luminescent material, so that the driving voltage can be effectively reduced, the luminous efficiency can be improved, and the service life of the organic electroluminescent device can be prolonged. The display device provided by the application has excellent display effect.
Meanwhile, the preparation process of the compound is simple and feasible, raw materials are easy to obtain, and the compound is suitable for industrial production.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
In order to more clearly illustrate the examples of the present application or the technical solutions in the prior art, the following description will briefly explain the drawings used in the examples or the description of the prior art, and it is obvious that the drawings in the following description are only one embodiment of the present application, and other embodiments can be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
A first aspect of the present application provides a compound of formula (I):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 30 Aryl, C of (2) 3 -C 30 Is a heteroaryl group of (2)Radicals or NR 5 R 6 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra, where R 1 、R 2 、R 3 And R is 4 One of which is other than H, or R 1 、R 2 、R 3 And R is 4 Is not H and is the same; herein, R 1 、R 2 、R 3 And R is 4 One of which is other than H, meaning that the other three are all H, with only one substituent other than H. R is R 1 、R 2 、R 3 And R is 4 Is not H, meaning that the other two are H.
R 5 And R is 6 Each independently selected from C 6 -C 30 Aryl or C of (2) 3 -C 30 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra;
the heteroatoms on the heteroaryl groups are each independently selected from O, S, N;
the Ra's are each independently selected from deuterium, C 1 -C 6 Alkyl, C of (2) 3 -C 6 Cycloalkyl, phenyl, biphenyl, naphthyl or carbazolyl groups.
Preferably, R 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 18 Aryl, C of (2) 3 -C 18 Heteroaryl or NR of (C) 3 R 4 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra;
preferably, R 5 And R is 6 Each independently selected from C 6 -C 18 Aryl or C of (2) 3 -C 18 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra;
preferably, R 1 、R 2 、R 3 And R is 4 In the 3-6 and 3'-6' positions.
More preferably, R 1 、R 2 、R 3 And R is 4 When not H, each is independently selected from the following groups:
more preferably, R 5 And R is 6 Each independently selected from the following groups:
for example, the compound of formula (I) is selected from the following compounds:
a second aspect of the present application provides a light-emitting layer host material comprising at least one of the compounds provided herein, wherein R 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 30 Aryl, C of (2) 3 -C 30 Heteroaryl of (a).
A third aspect of the present application provides a light-emitting layer guest material comprising at least one of the compounds provided herein, wherein R 1 、R 2 、R 3 And R is 4 Each independently selected from H, NR 5 R 6 。
Fig. 1 shows a schematic view of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are disposed in this order from bottom to top.
It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, and the present application is not limited to this structure, and the light-emitting layer host material and guest material of the present application may be used for any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, etc., and these layers may be added or omitted depending on the specific circumstances in practical applications.
A fourth aspect of the present application provides an organic electroluminescent device comprising at least one of the light-emitting layer host material and the light-emitting layer guest material provided herein. In the present application, the kind and structure of the organic electroluminescent device are not particularly limited, and various types and structures of organic electroluminescent devices known in the art may be used as long as at least one of the light emitting layer host material and the light emitting layer guest material provided in the present application can be used.
The organic electroluminescent device of the present application may be a light emitting device having a top emission structure, and examples thereof include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a bottom light emitting structure, and examples thereof include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a double-sided light emitting structure, and examples thereof include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode structure sequentially formed on a substrate.
In the organic electroluminescent device of the present application, any material used for the layer in the prior art may be used for the other layers, except that the light-emitting layer contains at least one of the light-emitting layer host material and the light-emitting layer guest material provided in the present application.
For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of protection of the present application in any way. It is understood that all organic electroluminescent devices capable of using at least one of the emissive layer host material and the emissive layer guest material of the present application are within the scope of the present application.
In the present application, the substrate 1 is not particularly limited, and a conventional substrate used in the organic electroluminescent device in the related art, for example, glass, polymer material, glass with TFT devices, polymer material, and the like can be used.
In the present application, the material of the reflective anode electrode 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) Transparent conductive materials such as zinc oxide (ZnO) and Low Temperature Polysilicon (LTPS), metallic materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as PEDOT (poly 3, 4-ethylenedioxythiophene), and multilayer structures of the above materials, and the like may be used.
In the present application, the material of the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be employed, for example, the following p-type dopants may be employed:
in the present application, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and may be made using a Hole Transport Material (HTM) well known in the art. The number of layers of the hole transport layer 4 is not particularly limited and may be adjusted according to actual needs as long as the purpose of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more. For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material may be selected from at least one of the following HT-1 to HT-33 compounds:
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in the present application, the light emitting material in the light emitting layer 5 may include at least one of a light emitting layer host material and a light emitting layer guest material of the present application.
The light emitting layer 5 may also comprise a combination of at least one of the light emitting layer host materials of the present application with at least one of the following known host materials (GPH).
For example, the known host material of the light-emitting layer may be selected from at least one of the following BH-1 to BH-36 compounds:
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the light-emitting layer 5 may also comprise a combination of at least one of the light-emitting layer guest materials of the present application with at least one of the following known guest materials.
For example, known emissive layer guest materials may be selected from at least one of the following BD-1 to BD-23 compounds:
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in the present application, the amount of the guest material in the light emitting layer 5 is not particularly limited, and may be an amount known to those skilled in the art.
In the present application, the material of the electron transport layer 6 is not particularly limited, and may be made of an electron transport material known in the art. The number of layers of the electron transport layer 6 is not particularly limited and may be adjusted according to actual needs as long as the purpose of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more. For example, the electron transport layer material may be selected from at least one of the following ET-1 to ET-59 compounds:
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in the present application, the electron transport layer 6 may further include n-type dopants, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
in the present application, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, for example, may include, but not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
In the present application, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
A fifth aspect of the present application provides a display device, which includes the organic electroluminescent device provided herein. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be employed, for example, the present application may be prepared using the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection material on the reflective anode electrode 2 as a hole injection layer 3;
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 as a hole transport layer 4;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer 5 comprises a host material and a guest material;
(5) Vacuum evaporating an electron transport material on the light-emitting layer 5 as an electron transport layer 6;
(6) Vacuum evaporating electron injection material selected from LiQ, liF, naCl, csF, li as electron injection layer 7 on electron transport layer 6 2 O、Cs 2 CO 3 One or a combination of a plurality of materials such as BaO, na, li, ca;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
Only the structure of a typical organic electroluminescent device and a method of manufacturing the same are described above, and it should be understood that the present application is not limited to such a structure. The electron transport material of the present application may be used for an organic electroluminescent device of any structure, and the organic electroluminescent device may be prepared using any preparation method known in the art.
The method for synthesizing the compounds of the present application is not particularly limited, and may be synthesized by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthesis of intermediate A, B
Into a 5L three-necked flask were charged 170.07g of 1-chloro-2-iodo-4-nitrobenzene (0.6 mol), 200.31g of 2-nitrobenzeneboronic acid (1.2 mol), 17.28g of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (15 mmol), 172.5g of potassium carbonate (K) 2 CO 3 ) (1.25 mol), 2500ml of toluene, 850ml of ethanol and 850ml of water are introduced into the mixture, the mixture is boiled at 75 ℃ for reaction for 16 hours, and then the mixture is extracted with 2500ml of toluene and 8000ml of water, a toluene solution is taken, and the toluene solution is subjected to spin flash drying, petroleum ether is used for passing through a silica gel column, and then the spin flash drying is carried out, thus 117.03g of 2-chloro-2 ', 5-dinitro-1, 1' -biphenyl (0.42 mol) is obtained (reaction yield: 70%).
117.03g of 2-chloro-2 ', 5-dinitro-1, 1' -biphenyl (0) was charged into a reaction flask.42 mol), 3500ml of o-dichlorobenzene, 330.48g of triphenylphosphine (PPh) 3 ) (1.26 mol) was dissolved in 250ml of o-dichlorobenzene, placed in an isobaric titration funnel, slowly dropped into the reaction solution, introduced with nitrogen, reacted at 170℃for 6 hours, then cooled to 25℃and extracted with 3500ml of toluene and 10L of water, then toluene/o-dichlorobenzene solvent was distilled out, the product was taken out, dissolved in toluene to a solution, passed through a silica gel column, and then toluene was spin-flash-dried to obtain 64.22g of 4-chloro-1-nitro-9H-carbazole (0.26 mol) (reaction yield: 62%).
64.22g of 4-chloro-1-nitro-9H-carbazole (0.26 mol), 9.6g of activated carbon, 17.99g of ferric trichloride hexahydrate (0.067 mol), 208ml of toluene and 200ml of ethanol are added into a 2L three-port bottle, heating and refluxing are carried out under stirring, 278g (80 wt%) of hydrazine hydrate is placed in an isobaric titration funnel and slowly dripped, reflux reaction is carried out for 2 hours after dripping, sampling analysis (the conversion rate is more than 99.5%) is carried out, the reaction liquid is cooled to 30 ℃ and added with 200ml of toluene and 300ml of water, stirring is carried out for 30 minutes, filtration is carried out, a filter cake is leached with 60ml of toluene, the filtrate is rotationally evaporated and dried after extraction with toluene, the organic phases are combined, the filter cake is washed to be neutral, and drying is carried out, thus obtaining 51.26g of intermediate A (4-chloro-9H-carbazole-1-amino) (the reaction yield: 91%).
25.63g of intermediate A (0.118 mol), 250ml of tetrahydrofuran, 50ml (35 wt%) of HCl and 250ml of water are added into a reaction flask, the mixture is subjected to external bath at 0-5 ℃, 10.58g of sodium nitrite (0.15 mol) is dissolved in 40ml of water, then the mixture is dripped into the reaction solution, diazonium reaction is carried out for 1 hour, after monitoring the completion of the reaction by Thin Layer Chromatography (TLC), 2g of urea is added, excessive sodium nitrite is removed, 23.5g of potassium iodide (0.1416 mol) is added, reaction is carried out for 16 hours, after conversion is completed, 25ml (10 wt%) of sodium bisulfite solution is added, potassium iodide is removed, 300ml of ethyl acetate and 1000ml of water are added for extraction, spin flash drying is carried out, a silica gel column is adopted, toluene is used for washing, spin flash drying is carried out, and 28.98g of intermediate B (4-chloro-1-iodo-9H-carbazole) is obtained (reaction yield: 75%).
Synthesis of intermediate E, H
Into a 5L three-necked flask were charged 170.07g of 1-chloro-3-iodo-5-nitrobenzene (0.6 mol), 200.31g of 2-nitrobenzeneboronic acid (1.2 mol), 17.28g of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (15 mmol), 172.5g of potassium carbonate (K) 2 CO 3 ) (1.25 mol), 2500ml of toluene, 850ml of ethanol and 850ml of water are introduced into the mixture, the mixture is boiled at 75 ℃ for reaction for 16 hours, and then the mixture is extracted with 2500ml of toluene and 8000ml of water, a toluene solution is taken, and the toluene solution is subjected to spin flash drying, petroleum ether is used for passing through a silica gel column, and then the spin flash drying is carried out, thus 117.03g of 2-chloro-2 ', 5-dinitro-1, 1' -biphenyl (0.42 mol) is obtained (reaction yield: 70%).
117.03g of 3' -chloro-2, 5' -dinitro-1, 1' -biphenyl (0.42 mol) and 3500ml of o-dichlorobenzene were charged into a reaction flask, and 330.48g of triphenylphosphine (PPh) 3 ) (1.26 mol) was dissolved in 250ml of o-dichlorobenzene, placed in an isobaric titration funnel, slowly dropped into the reaction solution, introduced with nitrogen, reacted at 170℃for 6 hours, then cooled to 25℃and extracted with 3500ml of toluene and 10L of water, then toluene/o-dichlorobenzene solvent was distilled out, the product was taken out, dissolved in toluene to a solution, passed through a silica gel column, and then toluene was spin-flash-dried to obtain 29.6g of 3-chloro-1-nitro-9H-carbazole (0.12 mol) (reaction yield: 28.57%) and 34.53g of 1-chloro-3-nitro-9H-carbazole (0.14 mol) (reaction yield: 33.33%).
29.6g of 3-chloro-1-nitro-9H-carbazole (0.12 mol), 4.43g of activated carbon, 8.3g of ferric trichloride hexahydrate (0.03 mol), 100ml of toluene and 100ml of ethanol are added into a 1L three-necked flask, heating and refluxing are carried out at 76 ℃ under stirring, 109.4g (80 wt%) of hydrazine hydrate is placed in an isobaric titration funnel, dropwise added, after the dropwise adding, refluxing is carried out for 2 hours, sampling analysis (the conversion rate is greater than 99.5%), cooling the reaction liquid to 30 ℃, adding 200ml of toluene and 300ml of water, stirring for 30 minutes, filtering, leaching a filter cake with 60ml of toluene, extracting the filtrate with toluene, rotationally steaming and drying, merging the organic phases, washing the filter cake to be neutral, and drying to obtain 23.66g of intermediate E (3-chloro-9H-carbazole-1-amino) (the reaction yield: 91%).
Into a 5L three-necked flask were charged 170.07g of 4-chloro-2-iodo-1-nitrobenzene (0.6 mol), 200.31g of 3-nitrobenzeneboronic acid (1.2 mol), 17.28g of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (15 mmol), 172.5g of potassium carbonate (K) 2 CO 3 ) (1.25 mol), 2500ml of toluene, 850ml of ethanol and 850ml of water are introduced into the mixture, the mixture is boiled at 75 ℃ for reaction for 16 hours, and then the mixture is extracted with 2500ml of toluene and 8000ml of water, a toluene solution is taken, and the toluene solution is subjected to spin flash drying, petroleum ether is used for passing through a silica gel column, and then the spin flash drying is carried out, thus 117.03g of 2-chloro-2 ', 5-dinitro-1, 1' -biphenyl (0.42 mol) is obtained (reaction yield: 70%).
Into a reaction flask were charged 117.03g of 5-chloro-2, 3 '-dinitro-1, 1' -biphenyl (0.42 mol) and 3500ml of o-dichlorobenzene, 330.48g of triphenylphosphine (PPh) 3 ) (1.26 mol) was dissolved in 250ml of o-dichlorobenzene, placed in an isobaric titration funnel, slowly dropped into the reaction solution, introduced with nitrogen gas, reacted at 170℃for 6 hours, then cooled to 25℃and extracted with 3500ml of toluene and 10L of water, then toluene/o-dichlorobenzene solvent was distilled out, the product was taken out, dissolved in toluene to obtain a solution, passed through a silica gel column, and then toluene was spin-flash-dried to obtain 29.6g of 6-chloro-1-nitro-9H-carbazole (0.12 mol) (reaction yield: 28.57%) and 34.53g of 3-chloro-6-nitro-9H-carbazole (0.14 mol) (reaction yield: 33.33%).
29.6G of 4-chloro-1-nitro-9H-carbazole (0.12 mol), 4.43G of activated carbon, 8.3G of ferric trichloride hexahydrate (0.03 mol), 100ml of toluene and 100ml of ethanol are added into a 1L three-necked flask, heating and refluxing are carried out at 76 ℃ under stirring, 109.4G (80 wt%) of hydrazine hydrate is placed in an isobaric titration funnel, dropwise adding is carried out slowly, refluxing reaction is carried out for 2 hours after the dropwise adding, sampling analysis (the conversion rate is greater than 99.5%), cooling is carried out to 30 ℃, 200ml of toluene and 300ml of water are added, stirring is carried out for 30 minutes, filtration is carried out, a filter cake is leached by 60ml of toluene, the filtrate is rotationally evaporated and dried after extraction by toluene, the organic phases are combined, the filter cake is washed to be neutral, and the intermediate G (6-chloro-9H-carbazole-1-amino) (the reaction yield: 91%) of 23.66G is obtained after the filter cake is dried.
11.83G of intermediate G (0.0546 mol), 150ml of tetrahydrofuran, 25ml (35 wt%) of HCl and 150ml of water are added into a reaction flask, the mixture is subjected to external bath at 0-5 ℃, 4.79G of sodium nitrite (0.069 mol) is dissolved in 20ml of water, then the mixture is dripped into the reaction solution, diazonium reaction is carried out for 1 hour, after monitoring the completion of the reaction by Thin Layer Chromatography (TLC), 1G of urea is added, excess sodium nitrite is removed, 10.76G of potassium iodide (0.0648 mol) is added, reaction is carried out for 16 hours, after conversion is completed, 13ml (10 wt%) of sodium bisulfite solution is added, potassium iodide is removed, 150ml of ethyl acetate and 500ml of water are added for extraction, spin flash drying is carried out, a silica gel column is adopted, toluene is used for washing, spin flash drying is carried out, and 13.41G of intermediate H (6-chloro-1-iodo-9H-carbazole) is obtained (reaction yield: 75%).
The above intermediate A, B, E, H can be synthesized repeatedly by the above method to obtain the desired amount, which is used in the following synthesis examples.
Synthetic examples
Synthesis of Compound C2
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 17.5gBis (3, 4-dimethylphenyl) amine (0.0777 mol), 0.339g Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1,48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours, and then water was added thereto for crystallization, followed by filtration, water washing, ethanol washing and further drying, and the mixture was passed through a silica gel column to obtain 24.32g of Compound C2 (0.03 mol) (reaction yield: 82%).
Synthesis of Compound C4
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 17.5g of 4-isopropyl-N-p-methylaniline (0.0777 mol), 0.339g of Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1.48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours under nitrogen, and then crystallized by adding water, filtered, washed with water, washed with ethanol, dried and passed through a silica gel column to obtain 24.32g of Compound C4 (0.03 mol) (yield: 82%)。
Synthesis of Compound C6
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 25.6g of 6-tert-butyl-N-o-tolyldibenzo [ b, D ]]Furan-4-amine (0.0777 mol), 0.339g Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1.48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours under nitrogen, and then water was added thereto for crystallization, followed by filtration, water washing, ethanol washing, drying and passage through a silica gel column to obtain 30.64g of Compound C6 (0.03 mol) (reaction yield: 81%).
Synthesis of Compound C12
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Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 27.78g of 6-cyclohexyl-N-phenyldibenzo [ a, c ]]Thiophene-4-amine (0.0777 mol), 0.339g Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1.48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours under nitrogen, and then water was added thereto for crystallization, followed by filtration, water washing, ethanol washing and further drying, followed by passage through a silica gel column to obtain 31.95g of Compound C12 (0.03 mol) (reaction yield: 81%).
Synthesis of Compound C16
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol) and 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 24.66g of N- (4-isopropylphenyl) dibenzo [ b, D ]]Thiophene-4-amine (0.0777 mol), 0.339g Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1.48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours, and then water was added thereto for crystallization, followed by filtration, water washing, ethanol washing and further drying, and the mixture was passed through a silica gel column to obtain 29.91g of Compound C16 (0.03 mol) (reaction yield: 82%).
Synthesis of Compound C18
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P)(0.002mol)、1922g of sodium tert-butoxide (0.2 mol) and 400ml of toluene were reacted at 110℃for 16 hours with nitrogen, then cooled to 25℃and extracted with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 19.27g of (4- (naphthylacetamide-1-yl) phenyl) boronic acid (0.0777 mol), 0.427g of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (0.37 mmol), 20.42g of potassium carbonate (K) 2 CO 3 ) (0.148 mol), 250ml of toluene, 100ml of ethanol and 100ml of water were introduced into the mixture, and after boiling reaction was performed at 75℃for 16 hours, the mixture was extracted with 500ml of toluene and 2000ml of water, a toluene solution was obtained, and the mixture was passed through a silica gel column, spin flash drying and passing through a silica gel column to obtain 23.05g of Compound C18 (0.03 mol) (reaction yield: 82%).
Synthesis of Compound C20
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate D (0.037 mol), 19.27g of (4- (naphthylacetamide-2-yl) phenyl) boronic acid (0.0777 mol), 0.427g of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (0.37 mmol), 20.42g of potassium carbonate (K) 2 CO 3 ) (0.148 mol), 250ml of toluene, 100ml of ethanol and 100ml of water were introduced into the mixture, and after boiling reaction was performed at 75℃for 16 hours, the mixture was extracted with 500ml of toluene and 2000ml of water, a toluene solution was obtained, and the mixture was passed through a silica gel column and then subjected to spin flash drying to obtain 23.61g of Compound C20 (0.031 mol) (reaction yield: 84%).
Synthesis of Compound C34
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 4-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) of tributyl phosphorus ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate C (0.092 mol) (reaction yield: 92%).
38.3g of intermediate C (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate D (0.037 mol) (reaction yield: 40%).
Adding into a reaction bottle15.6g of intermediate D (0.037 mol), 28.69g of 9-phenyl-2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9H-carbazole (0.0777 mol), 0.42g of Pd (PPh) 3 ) 4 (0.37 mmol), 20.42g K 2 CO 3 (1.48 mol), 300ml of dimethylformamide and 100ml of water were introduced into the mixture, and the mixture was boiled at 102℃for 16 hours, then, water was added thereto for crystallization, and the mixture was filtered, washed with water, washed with ethanol, and dried, followed by passing the mixture through a silica gel column to obtain 26.03g of Compound C34 (0.031 mol) (reaction yield: 84%).
Synthesis of Compound C43
Into a 1L three-necked flask were charged 21.6g of 3-chloro-9H-carbazol-1-amine (0.1 mol), 32.75g of 6-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) tributylphosphine ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen are introduced, after reaction for 16 hours at 110 ℃, the temperature is reduced to 25 ℃, the mixture is extracted with 500ml of toluene and 1000ml of water, a toluene solution is taken and passed through a silica gel column, and the mixture is dried by spin flash evaporation to obtain 38.3g of intermediate I (0.092 mol) (reaction yield: 92%).
38.3g of intermediate I (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate J (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate J (0.037 mol), 13.15g of diphenylamine (0.0777 mol), 0.339g of Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1.48 mmol), 14.22g of sodium tert-butoxide (0.148 mol), 400ml of toluene, nitrogen, boiling at 110 ℃ for 16 hours, adding water for crystallization, filtering, washing with water, washing with ethanol, drying, and passing through a silica gel column21.17g of Compound C43 (0.03 mol) was obtained (reaction yield: 83%).
Synthesis of Compound C44
Into a 1L three-necked flask were charged 21.6g of 4-chloro-9H-carbazole 1-amine (0.1 mol), 32.75g of 6-chloro-1-iodo-9H-carbazole (0.1 mol), and 0.46g of dibenzyl acetone dipalladium (Pd) 2 (dba) 3 ) (0.5 mmol), 4ml (10 wt%) tributylphosphine ((t-Bu)) 3 P) (0.002 mol), 19.22g of sodium tert-butoxide (0.2 mol), 400ml of toluene and nitrogen were introduced, after reaction at 110℃for 16 hours, the temperature was lowered to 25℃and extraction was carried out with 500ml of toluene and 1000ml of water, and a toluene solution was taken and passed through a silica gel column and dried by spin flash evaporation to obtain 38.3g of intermediate K (0.092 mol) (reaction yield: 92%).
38.3g of intermediate K (0.092 mol), 500ml of methylene chloride and 50.6g of triethylamine (0.5 mol) were put into a reaction flask, the mixture was subjected to external bath at-30℃and 27.55g of boron tribromide (0.11 mol) was slowly dropped into the reaction mixture, the temperature was naturally raised to 50℃after the completion of the dropping until the completion of the reaction (reaction time: about 5 to 6 hours), and after the completion of the reaction, the mixture was washed with water and ethanol by filtration to give 15.6g of intermediate L (0.037 mol) (reaction yield: 40%).
Into a reaction flask were charged 15.6g of intermediate L (0.037 mol), 17.5g of diphenylamine (0.0777 mol), 0.339g of Pd 2 (dba) 3 (0.37 mmol), 2.98g (10 wt%) of tri-tert-butylphosphine ((t-Bu)) 3 P) (1,48 mmol), 14.22g of sodium tert-butoxide (0.148 mol) and 400ml of toluene were boiled at 110℃for 16 hours, and then water was added thereto for crystallization, followed by filtration, water washing, ethanol washing and further drying, and the mixture was passed through a silica gel column to obtain 21.43g of Compound C44 (0.03 mol) (reaction yield: 84%).
The materials selected in examples 1-10 and comparative example 1 were selected from the following compounds:
example 1
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer with the thickness of 130nm in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
then placing the above-mentioned glass substrate with anode in vacuum cavity, vacuumizing to less than 10 -5 Vacuum evaporating a hole injection layer on the anode layer film, wherein the material of the hole injection layer is HI-1, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 5nm;
then, vacuum evaporating a hole transport material HT-1 as a hole transport layer A on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 80nm;
then, vacuum evaporating a hole transport material HT-2 as a hole transport layer B on the hole transport layer A, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
then, a light-emitting layer is vacuum-evaporated on the hole transport layer B, wherein the light-emitting layer comprises a host material C18 and a guest material BD-1 with the mass ratio of 4%, and evaporation is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation rate of the host material C18 is regulated to be 0.1nm/s, the evaporation rate of the guest material BD-1 is 4% of the evaporation rate of the host material C18, and the evaporation film thickness is 200nm;
then, vacuum evaporating an electron transport material ET-1 on the light-emitting layer to serve as an electron transport layer A, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
then, vacuum evaporating an electron transport material ET-2 as an electron transport layer B on the electron transport layer A, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 15nm;
then, vacuum evaporating LiF on the electron transport layer B as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
then, an Al layer was vacuum-deposited on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the deposition rate was 1nm/s and the deposition film thickness was 80nm.
Example 2
The procedure of example 1 was repeated except that the host material for the light-emitting layer was C20.
Example 3
The procedure of example 1 was repeated except that C34 was used as the host material for the light-emitting layer.
Example 4
The procedure of example 1 was repeated except that BH-1 was used as the host material for the light-emitting layer and C2 was used as the guest material for the light-emitting layer.
Example 5
The procedure of example 4 was repeated except that C4 was used as the guest material for the light-emitting layer.
Example 6
The procedure of example 4 was repeated except that C6 was used as the guest material for the light-emitting layer.
Example 7
The procedure of example 4 was repeated except that C12 was used as the guest material for the light-emitting layer.
Example 8
The procedure of example 4 was repeated except that C16 was used as the guest material for the light-emitting layer.
Example 9
The procedure of example 4 was repeated except that C43 was used as the guest material for the light-emitting layer.
Example 10
The procedure of example 4 was repeated except that C44 was used as the guest material for the light-emitting layer.
Comparative example 1
The procedure of example 1 was repeated except that BH-1 was used as the host material for the light-emitting layer.
The organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the organic electroluminescent devices prepared in examples 1 to 10 and comparative example 1 were measured using a digital source meter and a luminance meter under the same luminanceSpecifically, the driving voltage of the organic electroluminescent device was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent device was measured to be 5000cd/m 2 The voltage at that time is the driving voltage; the External Quantum Efficiency (EQE) and the wavelength (PL) of the organic electroluminescent devices prepared in examples 1 to 10 and comparative example 1 were measured using an EL spectrometry instrument (manufacturer: F-Star, model: PR 670). The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance results
As can be seen from table 1, compared with comparative example 1, the compounds C18, C20, and C34 prepared in this application are used as the host material of the light emitting layer of the organic electroluminescent device and the compounds C2, C4, C6, C12, C16, C43, and C44 prepared in this application are used as the guest material of the light emitting layer of the organic electroluminescent device, which can effectively reduce the driving voltage of the organic electroluminescent device, improve the EQE of the blue organic electroluminescent device, and are high-efficiency blue light emitting materials with good performance.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (8)

1. A compound of formula (I):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 18 Aryl, C of (2) 3 -C 18 Heteroaryl or NR of (C) 5 R 6 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra, where R 1 、R 2 、R 3 And R is 4 One of which is other than H, or R 1 、R 2 、R 3 And R is 4 Is not H and is the same; r is R 1 、R 2 、R 3 And R is 4 In the 3-6 and 3'-6' positions;
R 5 and R is 6 Each independently selected from C 6 -C 18 Aryl or C of (2) 3 -C 18 The hydrogen atom on the aryl or heteroaryl group may be substituted with Ra;
the heteroatoms on the heteroaryl groups are each independently selected from O, S, N;
the Ra's are each independently selected from deuterium, C 1 -C 6 Alkyl, C of (2) 3 -C 6 Cycloalkyl, phenyl, naphthyl or carbazolyl groups.
2. The compound according to claim 1, wherein R 1 、R 2 、R 3 And R is 4 When not hydrogen, each is independently selected from the following groups:
3. the compound according to claim 1, wherein said R 5 And R is 6 Each independently selected from the following groups:
4. a compound, wherein the compound is selected from the group consisting of:
5. a light-emitting layer host material comprising at least one of the compounds according to claim 1, wherein R 1 、R 2 、R 3 And R is 4 Each independently selected from H, C 6 -C 18 Aryl, C of (2) 3 -C 18 Heteroaryl of (a).
6. A light-emitting layer guest material comprising at least one of the compounds of claim 1, wherein R 1 、R 2 、R 3 And R is 4 Each independently selected from H, NR 5 R 6 。
7. An organic electroluminescent device comprising at least one of the light-emitting layer host material and the light-emitting layer guest material according to claim 5 or 6.
8. A display device comprising the organic electroluminescent device of claim 7.
CN202010739514.4A 2020-07-28 2020-07-28 Compound, luminescent material and organic electroluminescent device Active CN111909188B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160351811A1 (en) * 2015-06-01 2016-12-01 Universal Display Corporation Organic electroluminescent materials and devices
CN108586508A (en) * 2018-06-26 2018-09-28 烟台显华光电材料研究院有限公司 One kind is used as the multi-aromatic ring compound and its light-emitting device of electroluminescent material
CN109535187A (en) * 2017-09-22 2019-03-29 北京鼎材科技有限公司 Compound and application thereof and organic electroluminescence device
US20200111970A1 (en) * 2018-10-08 2020-04-09 Universal Display Corporation Organic electroluminescent materials and devices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160351811A1 (en) * 2015-06-01 2016-12-01 Universal Display Corporation Organic electroluminescent materials and devices
CN109535187A (en) * 2017-09-22 2019-03-29 北京鼎材科技有限公司 Compound and application thereof and organic electroluminescence device
CN108586508A (en) * 2018-06-26 2018-09-28 烟台显华光电材料研究院有限公司 One kind is used as the multi-aromatic ring compound and its light-emitting device of electroluminescent material
US20200111970A1 (en) * 2018-10-08 2020-04-09 Universal Display Corporation Organic electroluminescent materials and devices

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